POWER STORAGE DEVICE AND SUPER CAPACITOR DEVICE
A power storage device includes a positive electrode and a negative electrode disposed opposite to the positive electrode. The positive electrode and the negative electrode are respectively disposed on at least one surface of a current collector foil. The positive electrode and the negative electrode respectively include an active material, a conductive auxiliary and an adhesive, wherein the active material includes a porous material, an oxidation-reduction electrode material, or combination thereof. At least one of the positive electrode and the negative electrode has a multilayer structure containing three or more layers. The concentration of the oxidation-reduction electrode material in the outmost layer of the multilayer structure is the lowest.
This application claims the priority benefits of Taiwan application serial no. 102145619, filed on Dec. 11, 2013, and Taiwan application serial no. 103139209, filed on Nov. 12, 2014. The entirety of each of the above-mentioned patent applications is hereby incorporated by reference herein and made a part of specification.
TECHNICAL FIELDThe technical field relates to a power storage device and a super capacitor (SC) device.
BACKGROUNDA super capacitor (SC) is also known as an electrical double layer capacitor (EDLC) device, which stores power in the form of electrostatic energy. Studies on SC in recent years have especially focused on its high power output performance as well as energy storage and conversion capabilities. The energy storage and conversion by means of EDLC both originate from an electrical double layer structure formed by electrostatic charge adsorption. With such electrical double layer mechanism, during repeated charge/discharge operations, almost no loss of electrolytic solution and electrode caused by electrochemical reaction takes place, and thus, excellent reversible power and long-term charge/discharge cycling performance retention are achieved. The long-term cycle life may reach several tens of thousand times.
Since an area of the electrical double layer has a direct influence on electrode capacity, the commonly used electrical double layer active materials generally have characteristics such as porousness and high specific surface area. The electrical double layer active materials are not only used for active materials for capacity increase, but also used in active material supports, electronic conductors, ionic intercalation and deintercalation structures, thermal conductors or current collector substrates and so on. In addition to the active material, in order to impart to the electrode material and the current collector substrate ideal interface impedance and workability of the electrode itself, addition of an adhesive is required.
However, the adhesive itself is usually not a good conductor of electricity. Moreover, stability of the adhesive due to potential variation during charge/discharge cycles considerably affects the performance of devices in long-term cycling and capacity retention.
In past studies on SC, with the aim of improving energy density, lithium-ion battery electrode materials and electrical double layer electrode materials are often mixed together for use. However, the two different kinds of materials in the same electrode layer usually lead to competition between lithium ions so that an expected synergistic effect on function cannot be achieved. Thus, many studies began to perform coating on the two kinds of electrodes for different uses separately so as to form a double layer electrode.
Nevertheless, the aforesaid studies paid less attention to the long-term cycling characteristic and power performance.
SUMMARYAccording to an exemplary embodiment of the disclosure, a power storage device at least includes a positive electrode and a negative electrode. The positive electrode and the negative electrode are respectively disposed on at least one surface of a current collector foil. The positive electrode and the negative electrode respectively include an active material, a conductive auxiliary and an adhesive. Moreover, the active material includes a porous material, an oxidation-reduction electrode material, or combination thereof. The positive electrode and the negative electrode respectively have a multilayer structure containing three or more layers. Moreover, the oxidation-reduction electrode material in the multilayer structure has a concentration distribution along a thickness direction, and the concentration of the oxidation-reduction electrode material in an outmost layer of the multilayer structure is the lowest.
According to another exemplary embodiment of the disclosure, a super capacitor device includes an anode, a cathode, a separation membrane and an electrolytic solution. The cathode includes a positive electrode and a current collector foil; the anode includes a negative electrode and a current collector foil. The separation membrane is located between the anode and the cathode. The positive electrode and the negative electrode respectively include an active material, a conductive auxiliary and an adhesive. Moreover, the active material includes a porous material, an oxidation-reduction electrode material, or combination thereof. The positive electrode and the negative electrode respectively have a multilayer structure containing three or more layers. Moreover, the oxidation-reduction electrode material in the multilayer structure has a concentration distribution along a thickness direction, and the concentration of the oxidation-reduction electrode material in an outmost layer of the multilayer structure is the lowest.
Several exemplary embodiments accompanied with figures are described in detail below to further describe the disclosure in details.
Referring to
The oxidation-reduction electrode material in the active material is classified into an oxidation-reduction electrode material of a positive electrode and an oxidation-reduction electrode material of a negative electrode. For example, the oxidation-reduction electrode material of a positive electrode includes a lithium cobalt-based oxide, a lithium manganese-based oxide, a lithium nickel-based oxide, a lithium iron-based oxide, lithium iron salts or a group thereof. Moreover, the oxidation-reduction electrode material of a positive electrode may also be a metal oxide such as MnO2, V2O5, Fe2O3, WO2, NbO2 or NbO. In addition, the oxidation-reduction electrode material of a negative electrode includes, e.g., a lithium titanium oxide, a titanium sulfide, or a group thereof. The above different kinds of oxidation-reduction electrode materials may be used solely or in combination of two or more kinds as long as they have the same polarity.
Furthermore, the positive and negative electrodes 102 have a multilayer structure 106 containing three or more layers. Although only one electrode structure is shown in
The oxidation-reduction electrode material in the multilayer structure 106 has a concentration distribution 110 along a thickness direction 108. The concentration of the oxidation-reduction electrode material in an outmost layer 106a of the multilayer structure 106 is the lowest. Although the concentration distribution 110 shown in
In addition, as shown in
The aforesaid electrode design provided by the disclosure reduces the interface impedance between components or layers in a mixed state of two different kinds of active materials, and as a result, AC impedance, DC impedance, power characteristics of the electrode as well as lifetime during long-term cyclic operation and impedance increase thus caused are all improved. The intermediate layer contains a large amount of the oxidation-reduction electrode material, which thus suppresses self-discharge of electrical double layer material and indirectly improves storage life and reduces energy loss. The outer layer that contacts the electrolytic solution contains a large amount of electrical double layer material, which thus reduces formation of a solid-electrolyte interphase (SEI) layer between a conventional oxidation-reduction material and the electrolytic solution, and indirectly reduces the cost of device activation.
Referring to
The aforesaid electrode design proposed by the another exemplary embodiment of the super capacitor device of the disclosure reduces the interface impedance between components or layers in a mixed state of two different kinds of active materials, and as a result, AC impedance, DC impedance, power characteristics of the electrode as well as lifetime during long-teen cyclic operation and impedance increase thus caused are all improved. The intermediate layer contains a large amount of the oxidation-reduction electrode material, which thus suppresses self-discharge of electrical double layer material and indirectly improves storage life and reduces energy loss. The outer layer that contacts the electrolytic solution contains a large amount of electrical double layer material, which thus reduces formation of a solid-electrolyte interphase (SEI) layer between a conventional oxidation-reduction material and the electrolytic solution, and indirectly reduces the cost of device activation. Moreover, the electrode structure having three or more layers with different concentrations of the oxidation-reduction electrode material is prepared on the current collector foil, which accordingly improves the capacity performance of devices through variation in conductivity and energy density.
The following describes several experiments carried out in order to verify the effect of the disclosure. However, the scope of the disclosure is not limited to the following experiments.
Preparation 1
1. Materials
(1) Oxidation-reduction electrode material: lithium manganese oxide (LiMn2O4), abbreviated as LM.
(2) Porous material: activated carbon, abbreviated as AC.
(3) Conductive auxiliary: ECP600, ECP300, KS6, and CNT.
(4) Adhesive: carboxymethyl cellulose (CMC), sodium form.
2. An electrode was prepared on an aluminum current collector foil according to composition ratios shown in Table 1 below. Experimental Example 1 includes the first to the third layers, Comparative Example 1 includes the second to the third layers, Comparative Example 2 includes the first to the second layers, and Comparative Example 3 includes the second layer only, wherein all those layers that contact the aluminum current collector foil have a lower layer rank.
Then, the electrode having a dry surface was rolled again to increase density thereof. Next, the completed electrode was sufficiently dried at 80° C. The electrode, Celgard 2320 as a separation membrane, negative lithium metal, and upper and bottom covers of the device were stacked together in a sealed inert atmosphere. Finally, sufficient electrolytic solution containing 1.3 M of LiPF6 (EC/DEC) was injected to perform a packaging process, thereby completing preparation of a power storage device.
Test 1
An AC impedance test was conducted on Experimental Example 1 and Comparative Examples 1 to 3, and results thereof are shown in
Test 2
A cyclic charge/discharge test was conducted on Experimental Example 1 and Comparative Example 2 to obtain a cyclic voltammogram as shown in
Test 3
A high-speed charge/discharge test was conducted on Experimental Example 1 and Comparative Examples 1 to 3, and results thereof are shown in Table 2 below.
From Table 2, it is known that even after high-speed charge/discharge operations, the disclosure still has a higher power retention.
Preparation 2
1. Materials
(1) Oxidation-reduction electrode material: lithium titanium oxide (Li4Ti5O12), abbreviated as LTO.
(2) Porous material: activated carbon, abbreviated as AC.
(3) Conductive auxiliary: Super P (conductive carbon black).
(4) Adhesive: polytetrafluoroethylene (PTFE).
2. An electrode was prepared on an aluminum current collector foil according to composition ratios shown in Table 3 below, wherein all of the first layers contacted the aluminum current collector foil.
Then, the electrode structure in Experimental Example 2 was observed by EDS, as shown in
Next, the electrode having a dry surface was rolled again to increase density thereof. Subsequently, the completed electrode was sufficiently dried at 80° C. The electrode, Celgard 2320 as a separation membrane, positive lithium metal, and upper and bottom covers of the device were stacked together in a sealed inert atmosphere. Finally, sufficient electrolytic solution containing 1.3 M of LiPF6 (EC/DEC) was injected to perform a packaging process, thereby completing preparation of a power storage device.
Test 4
A high-speed charge/discharge test was conducted on Experimental Example 2 and Comparative Examples 4 to 5, and results thereof are shown in Table 4 below.
From Table 4, it is known that when the disclosure is applied to the anode, similarly, after high-speed charge/discharge operations, the disclosure still has a higher power retention.
Preparation 3
1. Materials
(1) Oxidation-reduction electrode material: lithium manganese oxide (LiMn2O4), abbreviated as LM.
(2) Porous material: activated carbon, abbreviated as AC.
(3) Conductive auxiliary: Super P and KS6.
(4) Adhesive: polytetrafluoroethylene (PTFE).
2. An electrode was prepared on an aluminum current collector foil according to composition ratios shown in Table 5 below. Experimental Example 3 includes the first to the third layers, Comparative Example 6 includes the second to the third layers, Comparative Example 7 includes the first to the second layers, and Comparative Example 8 includes the first layer only. All those layers that contact the aluminum current collector foil have a lower layer rank.
Then, the electrode having a dry surface was rolled again to increase density thereof. Next, the completed electrode was sufficiently dried at 80° C. The electrode, Celgard 2320 as a separation membrane, negative lithium metal, and upper and bottom covers of the device were stacked together in a sealed inert atmosphere. Finally, sufficient electrolytic solution containing 1.1 M of LiPF6 (EC/DEC/EMC) was injected to perform a packaging process, thereby completing preparation of a power storage device.
Test 5
A high-speed charge/discharge test was conducted on Experimental Example 3 and Comparative Examples 6 to 8, and results thereof are shown in Table 6 below.
From Table 6, it is known that even after high-speed charge/discharge operations, the disclosure still has a higher power retention.
In summary, the electrode structure of the disclosure is an electrode structure prepared on a current collector foil and having three or more layers with different concentrations of the oxidation-reduction electrode material. Thus, by making the concentration of the oxidation-reduction electrode material on the outmost side the lowest, and making the concentration of the oxidation-reduction electrode material show a concentration distribution in the multilayer electrode structure, the capacity performance of devices may be improved.
It will be apparent to those skilled in the art that various modifications and variations can be made to the structure of the disclosed embodiments without departing from the scope or spirit of the disclosure. In view of the foregoing, it is intended that the disclosure cover modifications and variations of this disclosure provided they fall within the scope of the following claims and their equivalents.
Claims
1. A power storage device, at least comprising:
- a positive electrode; and
- a negative electrode disposed opposite to the positive electrode, wherein
- the positive electrode and the negative electrode are respectively disposed on at least one surface of a current collector foil,
- the positive electrode and the negative electrode respectively comprise an active material, a conductive auxiliary and an adhesive, and
- the active material comprises a porous material, an oxidation-reduction electrode material, or combination thereof,
- at least one of the positive electrode and the negative electrode has a multilayer structure containing three or more layers, wherein the oxidation-reduction electrode material in the multilayer structure has a concentration distribution along a thickness direction, and a concentration of the oxidation-reduction electrode material in an outmost layer of the multilayer structure is the lowest.
2. The power storage device according to claim 1, wherein the concentration distribution comprises at least one Gaussian distribution or at least one gradient distribution.
3. The power storage device according to claim 1, wherein the oxidation-reduction electrode material of the positive electrode comprises a lithium cobalt-based oxide, a lithium manganese-based oxide, a lithium nickel-based oxide, a lithium iron-based oxide, lithium iron salts or a group thereof.
4. The power storage device according to claim 1, wherein the oxidation-reduction electrode material of the positive electrode comprises a metal oxide.
5. The power storage device according to claim 4, wherein the metal oxide comprises MnO2, V2O5, Fe2O3, WO2, NbO2 or NbO.
6. The power storage device according to claim 1, wherein the oxidation-reduction electrode material of the negative electrode comprises a lithium titanium oxide, a titanium sulfide, or a group thereof.
7. The power storage device according to claim 1, wherein the porous material is one material selected from a group consisting of activated carbon, hard carbon, soft carbon, graphite, mesophasecarbon and carbon black, or a group thereof.
8. The power storage device according to claim 1, wherein the conductive auxiliary is one material selected from a group consisting of carbon nanotubes, carbon nanofibers, conductive graphite, graphene, carbon black and carbon nanocapsules, or a group thereof.
9. The power storage device according to claim 1, wherein the adhesive is one material selected from a group consisting of polyvinylidene fluoride (PvDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), polyvinylpyrrolidone, polyethylene oxide (PEO), carboxyl methyl cellulose (CMC), styrene-butadiene rubber (SBR), polyacrylate and polyacrylonitrile.
10. The power storage device according to claim 1, wherein the multilayer structure consists of an intermediate layer, and outer layers on upper and lower sides of the intermediate layer.
11. The power storage device according to claim 10, wherein a proportion of the oxidation-reduction electrode material in the outer layers is from more than 0 to 27 wt %, and a proportion of the oxidation-reduction electrode material in the intermediate layer is 30 to 60 wt %.
12. The power storage device according to claim 10, wherein a thickness ratio of the outer layer to the intermediate layer is 0.1 to 0.5.
13. The power storage device according to claim 1, wherein the power storage device comprises a lithium battery, a capacitor, a solar cell or a lead-acid battery.
14. A super capacitor device, comprising:
- a cathode, comprising a positive electrode and a current collector foil;
- an anode, comprising a negative electrode and a current collector foil;
- a separation membrane located between the anode and the cathode; and
- an electrolytic solution, wherein
- the positive electrode and the negative electrode respectively comprise an active material, a conductive auxiliary and an adhesive, and
- the active material comprises a porous material, an oxidation-reduction electrode material, or combination thereof,
- the positive electrode and the negative electrode respectively have a multilayer structure containing three or more layers, wherein the oxidation-reduction electrode material in the multilayer structure has a concentration distribution along a thickness direction, and a concentration of the oxidation-reduction electrode material in an outmost layer of the multilayer structure is the lowest.
15. The super capacitor device according to claim 14, wherein the concentration distribution comprises at least one Gaussian distribution or at least one gradient distribution.
16. The super capacitor device according to claim 14, wherein the oxidation-reduction electrode material of the positive electrode comprises a lithium cobalt-based oxide, a lithium manganese-based oxide, a lithium nickel-based oxide, a lithium iron-based oxide, lithium iron salts or a group thereof.
17. The super capacitor device according to claim 14, wherein the oxidation-reduction electrode material of the positive electrode comprises a metal oxide.
18. The super capacitor device according to claim 17, wherein the metal oxide comprises MnO2, V2O18, Fe2O3, WO2, NbO2 or NbO.
19. The super capacitor device according to claim 14, wherein the oxidation-reduction electrode material of the negative electrode comprises a lithium titanium oxide, a titanium sulfide, or a group thereof.
20. The super capacitor device according to claim 14, wherein the porous material is one material selected from a group consisting of activated carbon, hard carbon, soft carbon, graphite, mesophasecarbon and carbon black, or a group thereof.
21. The super capacitor device according to claim 14, wherein the conductive auxiliary is one material selected from a group consisting of carbon nanotubes, carbon nanofibers, conductive graphite, graphene, carbon black and carbon nanocapsules, or a group thereof.
22. The super capacitor device according to claim 14, wherein the adhesive is one material selected from a group consisting of polyvinylidene fluoride (PvDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), polyvinylpyrrolidone, polyethylene oxide (PEO), carboxyl methyl cellulose (CMC), styrene-butadiene rubber (SBR), polyacrylate and polyacrylonitrile.
23. The super capacitor device according to claim 14, wherein the multilayer structure consists of an intermediate layer and outer layers on upper and lower sides of the intermediate layer.
24. The super capacitor device according to claim 23, wherein a proportion of the oxidation-reduction electrode material in the outer layers is from more than 0 to 27 wt %, and a proportion of the oxidation-reduction electrode material in the intermediate layer is 30 to 60 wt %.
25. The super capacitor device according to claim 23, wherein a thickness ratio of the outer layer to the intermediate layer is 0.1 to 0.5.
Type: Application
Filed: Dec 10, 2014
Publication Date: Jun 11, 2015
Inventors: Yu-Wei Lin (Changhua County), Li-Duan Tsai (Hsinchu City), Chia-Chen Fang (Taipei City), Jenn-Yeu Hwang (Keelung City)
Application Number: 14/566,682